Modification of cellulosic materials with thiazine dioxide quaternary ammonium salts



Patented Jan. 31, 1967 3,301,632 MODIFICATION OF CELLULOSIC MATERIALS WITH THIAZINE DIOXIDE QUATERNARY AMMONIUM SALTS Albert C'. Perrino, Crauston, R.I., assignor to I.C.I./r-

ganics/Inc., Providence, R.I., a corporation of Rhode Island No Drawing. Filed Aug. 5, 1963, Ser. No. 300,091 12 Claims. (Cl. 8-116.2)

The present invention relates to the treatment of cellulosic-containing textiles with quaternary ammonium compounds in such a manner that a primary valence bond is formed with a cellulosic textile.

Cell-ulosic textiles are treated with many chemical agents for improving dye receptivity, providing a soft handle and the like. However, such agents are often only attached to the textile by physical bonds or hydrogen bonding and, consequently, they are removed in laundering, dry cleaning and similar operations associated with normal use. An object of the present invention is to provide a means for bonding a treating agent to a cellulosic textile by primary chemical bonds which are not severed in such normal use. The treating agents may improve softness or water repellen-cy or lanimalize the fabric to provide better dye receptivity. It is also possible to provide chromophoric groups or dyestuif moieties in the treating agent itself which then can actually color the fabric without a separate dyeing treatment.

The treating agents employed in the present invention are quaternary ammonium derivatives of 1,4-thiazane- 1,1-dioxides (thiamorpholine dioxides) having the general formula i (if). R

/H a C-H in which: R is a branched or straight-chain alkyl group atoms at the 2 and 6 positions of the t-hiazane ring (e.g.,

containing chromophoric group);

R is hydrogen or a methyl group; and X is an anion, preferably singly charged, such as a halide, preferably chloride, bromide or iodide, alkyl phosphates, borates or alkyl sulfates having the formula in which R is a straight chained or branched alkyl group having about 1 to 18 carbon atoms or aryl sulfonatessuch as benzene sulfonate or toluene sulfonate; and n=1 or 2.

tiles and are reacted in the presence of an alkaline (acid I binding) agent having a K value less than 9.2. Suitable alkaline agents are hydroxides, carbonates and bicarbonates of most metals such as alkali and alkaline earth metals, and ammonium hydroxide, etc. These include sodium hydroxide, sodium carbonate and sodium bicarbonate.

The alkali may be added with the treating agent or after the fabric has been immersed in the solution or dispersion containing the treating agent. The fabric is then usually dried and allowed to stand at a suitable temperature for a period of time. It is not necessary to dry the fabric, however, as fabrics have been successfully treated by allowing the sample to stand in the treating bath. Excellent results have been obtained with temperatures ranging from 25 C. to C., although other tempera tures may be used. The time of treatment also will vary,

generally increasing as the temperature is lowered. Suitadipamide and polycaproamide), Dacron (polyethylene terephthalate), Ac-ril an (an acrylic), etc. and the like.

The word textile as generally used includes in its meaning filaments, fibers, threads, yarns, etc., such as are in woven, non-woven, knit, or otherwise formed fabrics, sheets, cloths and the like.

After the cure is completed, the textile may be washed with water or dilute acid, to remove excess alkali and with a solvent or water containing a surfactant to remove unused treating agents.

The elfect of the treatment depends upon the nature of the treating agent. For example, when R is an alkyl group having 12 or more carbon atoms, the treated fabric is water repellent and exhibits a soft pleasing handle. If R contains a dyestulf moiety or chromophoric group, the treated fabric is dyed. This is illustrated by the use of N-p-phenylazophenoxypropyl N ethyl-1,4-thiamorph0linium-l,l-dioxide iodide which colors cotton yellow. Other dyestuff moieties which may be used include those derived from azo, disazo, triazo, polyazo, diaryl and Hi arylmethane, quinoneimine such as indophenols, indoanilines, indamine, oxazine, acridines, methines, azomethines, thiazines and azines, quinone, chromone, sulfur, indigo, thioindig-o, anthraquinoneimine, flavanthrone, benzanthrone, phthalocyanine and other dyes which are generally stable to alkaline conditions as would be encountered during the curing stage of the above process.

Another effect is illustrated by N-methyl-N-ethy-l-1,4- thi-arnorpholinium-1,1-dioxide iodide, in which R is ethyl and R is hydrogen, n=1, which animalizes the fabric so that it can be dyed with acid dyes.

It is also possible to demonstrate that a primary valence bond is formed between the treating agents and the cellulosic textile.

The treated cellulosics are extracted with solvents which dissolve the treating agents and products obtained :by decomposing them under alkaline conditions. Retention of the effects of the treating agents, as measured by ob- 'servation or elemental analysis of the cellulosic after such solvent extension, gives evidence that a primary valence bond has formed between the treating agent and the cellulosic.

One important'advantage of the present treating agents is that they are soluble or self-dispersing in aqueous systems. This permits easy use in industry. However, other solvents, e.g., dimethyl form-amide, aromatic hydrocarbons such as benzene, toluene and xylene, dimethyl sulfoxide, dimethyl acetamide, alcohols such as ethanol, n-propanol and isopropanol and ketones such as acetone may be used. In addition, the quaternary ammonium function is destroyed under the alkaline cure conditions, thereby eliminating any adverse effect when water repellency or resistance to water-borne stains is desired.

The treating agents themselves may be prepared by methods known to the art. For example, N-alkyl-1,4- thiazane-Ll-dioxide can be easily obtained by the reaction of primary amine with divinyl sulfone or 2-chloroethyl sulfone. The quaternary ammonium derivatives can be prepared by treating the free bases with alkyl mono-halides, alkyl di-halides and esters, such as alkyl sulfates or a'lkyl phosphates, etc.

The invention is illustrated but not limited by the following examples. In these, spray test ratings were rated in accordance with AATCC Standard Test method 22-52, which is described on pages 164 166 of volume 35 of the Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists.

EXAMPLE 1 Application of N-methyl-N-ethyl-I,4-thiamorphlinium- 1,1-dioxide iodide to cotton fabric A swatch of 80 X 80 cotton print fabric was immersed in a solution containing 9.0 g. of N-methyl-N-ethyl-1,4- thiamorpholinium-l,l-dioxide and 79.0 g. of water. A 50% sodium hydroxide solution (12.0 g.) was added, and the fabric was then squeezed to 120% pickup and then heated at 100 105 C. for 25 minutes. The sample was then rinsed free of alkali with warm water, washed for 5 minutes with 0.1% of a nonyl phenol/nine-rnole ethylene oxide iadduct, rinsed and dried. The increase in weight of the fabric was 3.4%. The sample was then given two extractions with boiling ethanol for minutes. The increase in weight of the fabric was reduced only slightly to 3.14%, indicating that the treating agent was bonded to the fabric by primary valance bonds.

EXAMPLE 2 Animalization of cotton fabric with N-methyl-N-ethyl-1,4- thiamorpholinium-l ,1 -dioxide iodide Swatches of cotton fabric were immersed in a solution containing 8% N-methyl-Nethyl-1,4-thiamorpholinium- 1,1-dioxide iodide, 6% sodium hydroxide and 86% water, squeezed to 120% pickup and treated for one hour at 25 C., 40 C. or 70 C. All the fabrics were then rinsed free of alkali, extracted five minutes with dilute acetic acid, extracted five minutes with dilute sodium bicarbonate, washed five minutes at 40 C. with 0.1% of a nonyl phenol/nine-mole ethylene oxide adduet, and ex- Samples I, II and III exhibited strong affinity for acid dyes and could be dyed to deep shades with Ahcoquinone Rubine R (C.I. Acid Red 80; Color Index, Part II, 68215), while the control was only stained.

EXAMPLE 3 Application of N-methyl-N-octadecyl-I,4-thiamorpholiniam-LJ-dioxide methosalfate to cotton with sodium carbonate A piece of 80 x 80 cotton fabric was immersed in a 2.5% dispersion of N-methyl-Noctadecyl-1,4-thiamorpholinium-1,1-dioxide methosulfate, squeezed to 120% pickup, air dried, immersed in a 2% solution of sodium carbonate, air dried and then heated at 155 C. for 3 minutes. The fabric was then washed for 10 minutes in a 0.1% sodium carbonate, 0.1% of a hexadecyl alcohol/eight-mole ethylene oxide adduct solution at 57-58 C., rinsed, extracted twice with boiling ethanol for 10 minutes and allowed to dry. The fabric exhibited a 50 spray test rating.

EXAMPLE 4 Application of N-methyl-N-dodecyl-I,4-thiamorpholinium-1,1-di0xide methosalfate to cotton with sodium bicarbonate A piece of x 80 cotton print fabric was immersed in a 4% aqueous solution of N-methyl-N-dodecyl-l,4- thiamorpholinium-l, l-dioxide methosulfate at 60 C., removed and allowed to air dry. The fabric was then immersed in a 5% solution of sodium bicarbonate, removed, air dried and heated at 150.-160 C. for 5 minutes. The fabric was rinsed free of alkali with Water at 4050 C. and dried. The sample exhibited a marked water repellent etfect both before and after extraction with boiling ethanol.

EXAMPLE 5 Application of N-methyl-N-octadecyl-1,4-thiamorpholinium-1,1-dioxide methosulfate to cotton with sodium hydroxide A 10% aqueous dispersion of N-methyl-N-octadecyl- 1,4-thiamorpholin-ium-1,l-dioxide methosulf-ate was prepared at 55 C. and subsequently diluted with water to a 2% dispersion. A piece of fabric was immersed in the dispersion, squeezed to pickup, air dried, immersed in a 1% solution of sodium hydroxide, air dried and then heated at C. for 5 minutes. The fabric was then rinsed free from alkali and, after drying, exhibited a 50 spray rating. After extraction of the fabric with boiling ethanol, the spray rating remained 50, the fabric had a soft pleasing handle and exhibited a marked resistance to water-borne stains.

EXAMPLE 6 Dyeing of cotton with N-p-phenylazophenoxypropyl-N- ethyl-1,4-thiamorph0linium-1,1-dioxide iodide A piece of cotton fabric was immersed in a 3.8% solu tion of N-p-phenylazophenoxypropyl-N-ethyl-1,4-thiamorpholinium-1,1-dioxide iodide in dimethyl formamide, squeezed to 120% pickup and air dried. The fabric was then immersed in a 2% solution of sodium hydroxide, squeezed to 120% pickup, air dried, and heated at 100 C. for 15 minutes. The fabric was washed free of alkali in warm (50 C.) water, washed with dilute hydrochloric acid, washed with warm water until free from acid, washed with dilute sodium carbonate solution, given a final rinse with warm water and air dried. The sample was extracted twice with dimethyl formamide at 9095 C. for 10 minutes, rinsed in water and air dried. The fabric was dyed a bright yellow which exhibited excellent light fastness as well as wash and perspiration fastness.

EXAMPLE 7 Dyeing of rayon with N-p-phenylazophenoxypropyl-N- ethyl-1,4-thiamorpholinium-1,Z-dioxide iodide A swatch of rayon fabric was immersed in a 3. 8% solution of N p phenylazophenoxypropyl-N-ethyl-1,4- thiamorpholinum-1,1-dioxide iodide in dimethyl fortnamide, squeezed to 120% pickup, air dried, immersed in a 2% solution of sodium hydroxide, squeezed to 120% pickup, air dried and heated at C. for 5 minutes. This fabric was then given the wash and extraction treatments described in Example 1?. The yellow fabric so obtained exhibited excellent resistance to solvents and washing with detergents.

EXAMPLE 8 Dyeing of cotton with N-p-phenylazophenoxypropyl-N- ethyl-1,4-thiamorpholinum-1 ,1 -dioxide bromide 80 x 80 cotton print fabric was immersed in a 4% dimethyl formamide solution of N p-phenylazophenoxypropyl N ethyl-1,4-thiamorpholinium-l,l-dioxide bromide, squeezed to 120% pickup, immersed in a 2% solution of sodium hydroxide, squeezed to about 120% pickup and air dried. The fabric was then heated for 23 minutes at 125 C., rinsed sequentially in tap water, dilute hydrochloric acid, and dilute sodium bicarbonate, then rinsed in tap water and finally extracted twice in dimethyl formamide at 120 C. for minutes. A bright yellow fabric was obtained.

While the invention has been illustrated by specific examples, it will be appreciated that various changes and modifications may be made without departing from the scope of the invention as defined in the claims.

What is claimed is:

1. A process for the treatment of a cellulosic textile which comprises applying to the fabric a 1,4-thiazane-1,1-dioxide treating agent having the formula in which R is an alkyl group containing about 1 to 18 carbon atoms, R is a member of the group consisting of hydrogen and organic groups which do not render the hydrogen atom bonded to the carbon atom designated by an asterisk more acidic than hydrogen atoms attached to the carbon atoms at the 2 and 6 position of the thiazane ring, R is a member of the group consisting of hydrogen and methyl, X- is an anion, and n is 1-2,

and curing in the presence of an alkaline curing agent having a K less than 9.2.

2. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is dispersed in a liquid, and the fabric is soaked in the liquid to apply the treating agent.

3. A process for the treatment of a cellulosic textile as set forth in claim 2 in which the liquid is an aqueous medium.

4. A process for the treatment of a cellulosic textile as set forth in claim 3 in which the alkaline agent is also present in the aqueous medium and is soaked into the textile to be present when it is cured.

5. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the cure is effected at about 25-1 C. for about 360 minutes.

6. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the cure is effected at a temperature of about 1 00-1 60 C. for 5-15 minutes.

7. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is N- rnethyl-N-ethyl-1,4-thiarnorpholinium-1,l-dioxide iodide.

8. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is N- methyl N octadecyl-l,4-thiamorpholinium-1,l-dioxide methosulfate.

9. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is N- methyl N dodecyl 1,4-thiamorpholiniurn-1,1-dioxide methosulfate.

10. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is N-pphenylazophenoxypropyl N-ethyl-1,4-thiamorpholinium- 1,1-dioxide iodide.

11. A process for the treatment of a cellulosic textile as set forth in claim 1 in which the treating agent is N-pphenylazophenoxypropyl N-ethyl-1,4-thiamorpholinium- 1,1-dioxide bromide.

12. A cellulosic textile treated by the process of claim 1.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

I. C. CANNON, Assistant Examiner. 

1. A PROCESS FOR THE TREATMENT OF A CELLULOSIC TEXILE WHICH COMPRISES APPLYING TO THE FABRIC A 1,4-THIAZANE-1, 1-DIOXIDE TREATING AGENT HAVING THE FORMULA 